CN107681122A - A kind of three-dimensional grapheme Si MoS2The preparation method of composite - Google Patents
A kind of three-dimensional grapheme Si MoS2The preparation method of composite Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of three-dimensional grapheme Si MoS2The preparation method of composite, the described method comprises the following steps:1) three-dimensional grapheme is prepared;2) Si layers are deposited on three-dimensional grapheme;3) MoS is deposited on Si layers2, obtain three-dimensional grapheme Si MoS2Composite.Three-dimensional grapheme Si MoS provided by the invention2Composite, the specific surface area of its three-dimensional grapheme are higher by hundreds of thousands times, Si, MoS than two-dimensional graphene2Three-dimensional grapheme surface is uniformly distributed in, good dispersion, had so both avoided Si and MoS2Nano-particle is assembled in cyclic process, and and can effectively buffers its volumetric expansion in cyclic process, while also effectively prevent the accumulation again of graphene, so as to improve its cyclical stability;Lithium ion battery specific capacity produced by the present invention reaches 2000mAh/g, and initial coulomb efficiency reaches 82%, and putting specific capacity by more than 200 circulations does not substantially decay, and capability retention reaches 97%, shows excellent cyclical stability.
Description
Technical field
The present invention relates to a kind of preparation of lithium ion battery negative material, more particularly to a kind of three-dimensional grapheme-Si-MoS2
The preparation method of composite.
Background technology
Lithium ion battery has that voltage is high, memory-less effect higher than energy, has extended cycle life, the features such as non-environmental-pollution,
It is current most popular chargeable portable power source, up to now, it has been widely used in mobile phone, notebook computer, number
Mechanical, electrical sub- translater of code-phase etc..Lithium ion battery negative material is the core of current Study on Li-ion batteries.Business lithium from
The negative material of sub- battery is mostly graphite material.Graphite have crystallization layer structure, be easy to the insertion of lithium ion wherein and
Deintercalation, interlayer compound L iC6 is formed, is a kind of negative material of stable performance.But graphite cathode theoretical specific capacity is only
372mAh/g, limit the further development of lithium ion battery.
Existing Si has up to 4200mAh/g specific capacity, it appears that is preferable height ratio capacity and the negative pole of safety
Material, but Si has 320% Volume Changes during embedding lithium takes off lithium, this often leads to Si active material efflorescence, and from
Come off on the colelctor electrode of coating, lose charge-discharge characteristic.In addition, Si is a kind of intrinsic material, without doping or
If coating modification, its electric conductivity is poor more than carbon materials such as graphite, it is thus impossible to form effective conductive network, realization has
Imitate rapidly discharge and recharge.
MoS2It is hexagonal crystal system inorganic layered compounds, it forms stratiform by S-Mo-S element stacks, in layer between atom
By stable covalent key connection, and then combined between layers by weaker Van der Waals force.As lithium ion battery negative material,
MoS2Theoretical capacity reach 800mAh/g, its special layer structure be beneficial to lithium ion insertion and abjection.However, due to it
Low electrons/ions electrical conductivity itself and serious volumetric expansion during removal lithium embedded make it that its cyclical stability is extremely low.This
Outside, during cell reaction, MoS2 and Li+React and generate the Li of indissoluble2S, Li2S has been catalyzed the decomposition of electrolyte again
So as to the reason for polymeric layer for foring thick result in irreversible capacitance loss, and this is also its cyclical stability difference.
Therefore, it is necessary to research and develop a kind of composite for the advantages that cyclical stability is high, performance is good.
The content of the invention
Object of the present invention is to provide a kind of three-dimensional grapheme-Si-MoS2The preparation method of composite, it can
Solve the problems, such as that solution graphene is easily reunited, hardly possible is scattered, be difficult to obtain high-specific surface area, solution MoS2The particle in cyclic process
Easily aggregation and its volumetric expansion during lithium deintercalation the problems such as, solves efflorescence and the spallation problems of Si active materials.
To achieve the above object, the invention provides following technical scheme:
A kind of three-dimensional grapheme-Si-MoS2The preparation method of composite, the described method comprises the following steps:
1) three-dimensional grapheme is prepared;
2) Si layers are deposited on three-dimensional grapheme;
3) MoS is deposited on Si layers2, obtain three-dimensional grapheme-Si-MoS2Composite.
Preferably, the Si layers that deposited on three-dimensional grapheme deposit specifically by LPCVD methods:Three-dimensional grapheme is put
Enter LPCVD reative cells, be passed through protective gas, the protective gas is argon gas, hydrogen or helium, and flow is controlled in 300-
600sccm, the air pressure in reative cell is set to be maintained at 20-50Pa, temperature is maintained at 600-700 DEG C, when temperature reaches design temperature
Afterwards, toward being passed through SiH in reative cell4Reacting gas, flow control close reacting gas after 50-150sccm, reaction 30-300S
And protective gas, three-dimensional grapheme load Si layers are obtained after cooling, the thickness of the Si layers is 10-200nm.
Preferably, it is described to deposit MoS on Si layers2Specifically include:
It will form uniform reaction solution after molybdate, deionized water and thioacetyl amine solvent, the molybdate and go
The concentration of deionized water solution is 1-5mg/ml, and the mass ratio of the thioacetamide and molybdate is 1:1-1:5;
The three-dimensional grapheme for being loaded with Si layers is impregnated into reaction solution, by reaction solution at a temperature of 200-250 DEG C
Hydro-thermal reaction 20-30h;After reaction terminates, take out three-dimensional grapheme and rinse repeatedly;Three-dimensional grapheme is put into full of lazy after rinsing
In the environment of property gas shield, anneal 1-5h at a temperature of 320-400 DEG C, obtains uniformly bearing in the Si layer surfaces of three-dimensional grapheme
Carry MoS2Composite.
Preferably, the molybdate is sodium molybdate or ammonium molybdate.
Preferably, the inert gas is argon gas, nitrogen, or argon gas and nitrogen mixed gas.
Preferably, it is described that MoS is deposited on nano Si2Specifically by magnetron sputtering deposition MoS2:Deposition there are into Si layers
Three-dimensional grapheme is put into coating chamber, and coating chamber is vacuumized and three-dimensional grapheme is heated, when vacuum reaches 1 ×
10-4-1×10-3Pa, when temperature reaches 200-300 DEG C, working gas is passed through, gas flow is controlled in 20-500sccm, technique
Vacuum degree control sets 50-200W in 0.1-1Pa, target power output, and now working gas produces ionization, gas ion bombardment MoS2 targets
Material, target atom is spilt and is deposited on three-dimensional grapheme, sputtering time 1-10min;, finally give three-dimensional grapheme-Si-MoS2
Composite.
Preferably, the working gas is Ar gas.
Preferably, the three-dimensional grapheme for preparing comprises the following steps that:
1) substrate is provided;
2) under the conditions of the protection gas and hydrogen that flow velocity is 300-600s.c.c.m, 800~1300 DEG C of temperature, substrate is removed
Carbon-source gas are passed through after oxide layer again, 2-10 closes carbon-source gas after minute, by obtained sample using cooldown rate as
200-300 DEG C/min is cooled to room temperature, closes protection gas and hydrogen;
3) PMMA in the coating of the surface of obtained sample, then puts it into metal etch liquid and removes metallic substrates,
Rinsed again with deionized water;
4) above-mentioned sample is put into acetone or toluene, removes PMMA, then soaked successively clearly with ethanol, deionized water
Wash;
5) finally the sample cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity.
Preferably, described carbon-source gas be methane, methanol, ethanol or ethane in one or more, described protection
Gas is argon gas or neon.
Preferably, metal etch liquid is FeCl in the step 3)3Solution, ammonium persulfate or HCl and H2O2Mixing it is molten
Liquid.
Beneficial effects of the present invention:(1) three-dimensional grapheme-Si-MoS provided by the invention2Composite, its three-dimensional graphite
The specific surface area of alkene is higher by hundreds of thousands times, Si, MoS than two-dimensional graphene2Three-dimensional grapheme surface is uniformly distributed in, dispersiveness
It is good, so both avoided Si and MoS2Nano-particle is assembled in cyclic process, and and can effectively buffers it in cyclic process
Volumetric expansion, while the accumulation again of graphene is also effectively prevent, so as to improve its cyclical stability;(2) because MoS2It is special
Different layer structure, Si outer layer is placed on, not only improves the deintercalation of lithium ion, and can effectively buffers nano Si and is being circulated throughout
Volumetric expansion in journey, extend the life-span of battery;(3) lithium ion battery specific capacity produced by the present invention reaches 2000mAh/g, first
Secondary coulombic efficiency reaches 82%, and putting specific capacity by more than 200 circulations does not substantially decay, and capability retention reaches 97%, table
Reveal excellent cyclical stability;(4) even if lithium ion battery discharge and recharge under conditions of high current, electrode remains to keep stable
Circulation behavior, show excellent high rate capability.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of preparation method of the present invention;
Fig. 2 is three-dimensional grapheme-Si-MoS provided by the invention2Circulation of the composite under 100mA/g current densities
Curve map;
Fig. 3 is three-dimensional grapheme-Si-MoS provided by the invention2Discharge and recharge of the composite in different current densities follows
Ring curve map.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Three-dimensional grapheme material prepared by the present invention, the graphene of two dimension is structurally different from, it has three-dimensional hollow
Porous network structure, net wall are graphene, are the graphite of layer structure and porous graphitic carbon foam, have extremely-low density table
The advantages that area, high heat conduction, high temperature resistant, corrosion-resistant, ductility, good pliability, single-layer and transparent and quality is higher.
As shown in figure 1, preparation method preparation of the present invention is as follows:
S101:Prepare three-dimensional grapheme;
S102:Si layers are deposited on three-dimensional grapheme;
S103:MoS is deposited on Si layers2, obtain three-dimensional grapheme-Si-MoS2Composite.
The specific present invention can use implementation below:
Embodiment 1
1) three-dimensional grapheme is prepared:
Nickel screen (aperture 0.01mm) is placed in horizontal pipe furnace, is passed through argon gas (flow velocity 500s.c.c.m) and hydrogen
(200s.c.c.m.), under the conditions of 1000 DEG C, heat 10 minutes, after removing oxide layer, then be passed through methane gas
(5s.c.c.m.), after 5 minutes, methane gas is closed, keep the flow velocity of argon gas and hydrogen constant, by sample with 200 DEG C/min's
Speed is quickly cooled to room temperature, closes argon gas and hydrogen, and individual layer three-dimensional grapheme is made, and is applied on nickel screen/graphene-structured surface
PMMA on cloth;Then HCl and H are put it into2O2Volume ratio is 1:Metallic nickel is removed in 3 solution, one is rinsed with deionized water
Under;Then graphene/PMMA samples are put into acetone, PMMA is removed;Again with ethanol, deionized water successively soaking and washing
10min;Finally the three-dimensional grapheme cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity;
2) Si layers are deposited on three-dimensional grapheme;
Si layers are made by LPCVD (low-pressure chemical vapour deposition technique) method.LPCVD prepares nano Si layer process:Will
The above-mentioned three-dimensional grapheme 1) obtained is put into LPCVD reative cells, is passed through protective gas, and vacuumizing keeps the air pressure in reative cell
In 20Pa, 600 DEG C of temperature setting, after temperature reaches design temperature, it is passed through reacting gas and is reacted in setting time, reaction knot
Reacting gas and protective gas are closed after beam, the Si layers loaded on three-dimensional grapheme are obtained after cooling;Wherein, the protection gas
Body is argon gas, and flow is controlled in 300sccm;The reacting gas is SiH4Gas, flow are controlled in 50sccm;During the reaction
Between be 300S;The thickness of Si layers is 10nm;
3) reaction solution is prepared
By 30mg sodium molybdates (Na2MoO4·2H2) and 60mg thioacetamides (C O2H5NS) it is dissolved in 30ml deionized water
In, form uniform reaction solution;
4) three-dimensional grapheme is impregnated into reaction solution and carries out hydro-thermal reaction and annealing
The three-dimensional grapheme that step 2) is obtained is impregnated into the reaction solution that step 3) obtains, and solution is moved into polytetrafluoro
In the stainless steel cauldron of ethene inner bag, hydro-thermal reaction 28h is carried out at 200 DEG C;It is anti-with distilled water and ethanol after reaction terminates
Xian is floated again 3 times, sample is then put into 360 DEG C of annealing 3h in the environment full of argon gas;Finally give three-dimensional grapheme-Si-
MoS2 composites.
Embodiment 2
1) three-dimensional grapheme is prepared
Copper mesh (aperture 0.01mm) is placed in horizontal pipe furnace, is passed through argon gas (flow velocity 600s.c.c.m) and hydrogen
(250s.c.c.m.), under the conditions of 900 DEG C, heat 20 minutes, after removing oxide layer, then be passed through methane gas
(10s.c.c.m.), after 5 minutes, methane gas is closed, keep the flow velocity of argon gas and hydrogen constant, by sample with 250 DEG C/min
Speed be quickly cooled to room temperature, close argon gas and hydrogen, individual layer three-dimensional grapheme be made, on nickel screen/graphene-structured surface
PMMA in coating;Then HCl and H are put it into2O2Volume ratio is 1:Metallic nickel is removed in 3 solution, rinsed with deionized water
Once;Then graphene/PMMA samples are put into acetone, PMMA is removed;Again with ethanol, deionized water successively soaking and washing
10min;Finally the three-dimensional grapheme cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity;
2) Si layers are deposited on three-dimensional grapheme
Si layers are made by LPCVD (low-pressure chemical vapour deposition technique) method.LPCVD prepares nano Si layer process:Will
The above-mentioned three-dimensional grapheme 1) obtained is put into LPCVD reative cells, is passed through 500sccm helium, vacuumizes the air pressure made in reative cell
20Pa is maintained at, 620 DEG C of temperature setting, after temperature reaches 620 DEG C, is passed through 50sccm SiH4Gas, closed after reacting 60S
SiH4Gas, helium is closed, obtain loading about 10nm Si particles after cooling on three-dimensional grapheme;
3) MoS is deposited on Si layers2, obtain three-dimensional grapheme-Si-MoS2Composite
MoS is prepared using magnetron sputtering2:2) three-dimensional grapheme obtained is put into coating chamber, chamber is vacuumized
And substrate heating, base vacuum reach 1 × 10-4-1×10-3Pa, when the temperature of three-dimensional grapheme reaches 200-300 DEG C, lead to
Enter working gas, gas flow control sets 50- in 20-500sccm, technique vacuum degree control in 0.1-1Pa, target power output
200W, working gas produce ionization, gas ion bombardment target, target atom are spilt and is deposited in substrate, sputtering time 1-
10min;The plated film target is MoS2Target, the working gas are Ar gas, finally give three-dimensional grapheme-Si-MoS2It is compound
Material.
Three-dimensional grapheme-Si-MoS provided by the invention2Composite, because the Stability Analysis of Structures and super large of three-dimensional grapheme
Specific surface area, Si, MoS2Three-dimensional structure graphenic surface can be uniformly dispersed in, so both avoids Si, MoS2Particle is following
Assemble during ring, also effectively prevent the accumulation again of graphene sheet layer;MoS simultaneously2Special layer structure, beneficial to lithium ion
Deintercalation, Si is clipped in the middle, can effectively buffer the volumetric expansion of silicon and silicon in charge and discharge process and live by itself and three-dimensional grapheme
The efflorescence and peeling of property material.
By three-dimensional grapheme-Si-MoS made from above-mentioned specific embodiment2Negative pole of the composite as lithium ion battery
Lithium ion battery is made in material, and its specific capacity reaches 2000mAh/g, and first charge-discharge coulombic efficiency reaches 82%, more than 200
After secondary charge and discharge cycles, capacity is not substantially decayed, and coulombic efficiency is maintained at 97% or so, as shown in Figure 2;In different electricity
The charge and discharge cycles of current density also show excellent cycling stability, illustrate that it has good high rate performance, as shown in Figure 3.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. three-dimensional grapheme-Si-MoS2The preparation method of composite, it is characterised in that methods described includes following step Suddenly:1) three-dimensional grapheme is prepared;2) Si layers are deposited on three-dimensional grapheme;3) MoS is deposited on Si layers2, obtain three-dimensional grapheme-Si-MoS2Composite.
- 2. three-dimensional grapheme-Si-MoS according to claim 12The preparation method of composite, it is characterised in that described Si layers are deposited on three-dimensional grapheme to deposit specifically by LPCVD methods:Three-dimensional grapheme is put into LPCVD reative cells, is passed through Protective gas, the protective gas are argon gas, hydrogen or helium, and flow is controlled in 300-600sccm, makes the air pressure in reative cell Be maintained at 20-50Pa, temperature is maintained at 600-700 DEG C, after temperature reaches design temperature, toward reative cell in be passed through SiH4Reaction Gas, flow control close reacting gas and protective gas after 50-150sccm, reaction 30-300S, three are obtained after cooling Graphene-supported Si layers are tieed up, the thickness of the Si layers is 10-200nm.
- 3. three-dimensional grapheme-Si-MoS according to claim 12The preparation method of composite, it is characterised in that described MoS is deposited on Si layers2Specifically include:Uniform reaction solution, the molybdate and deionization will be formed after molybdate, deionized water and thioacetyl amine solvent The concentration of the aqueous solution is 1-5mg/ml, and the mass ratio of the thioacetamide and molybdate is 1:1-1:5;The three-dimensional grapheme for being loaded with Si layers is impregnated into reaction solution, by reaction solution at a temperature of 200-250 DEG C hydro-thermal React 20-30h;After reaction terminates, take out three-dimensional grapheme and rinse repeatedly;Three-dimensional grapheme is put into full of indifferent gas after rinsing In the environment of body protection, anneal 1-5h at a temperature of 320-400 DEG C, obtains uniform load in the Si layer surfaces of three-dimensional grapheme MoS2Composite.
- 4. three-dimensional grapheme-Si-MoS according to claim 32The preparation method of composite, it is characterised in that:It is described Molybdate is sodium molybdate or ammonium molybdate.
- 5. three-dimensional grapheme-Si-MoS according to claim 32The preparation method of composite, it is characterised in that:It is described Inert gas is argon gas, nitrogen, or argon gas and nitrogen mixed gas.
- 6. three-dimensional grapheme-Si-MoS according to claim 12The preparation method of composite, it is characterised in that described MoS is deposited on nano Si2Specifically by magnetron sputtering deposition MoS2:The three-dimensional grapheme that deposition there are Si layers is put into plated film Room, coating chamber is vacuumized and three-dimensional grapheme is heated, when vacuum reaches 1 × 10-4-1×10-3Pa, temperature reach During to 200-300 DEG C, be passed through working gas, gas flow control in 20-500sccm, technique vacuum degree control in 0.1-1Pa, Target power output sets 50-200W, and now working gas produces ionization, gas ion bombardment MoS2 targets, target atom is spilt into deposition On three-dimensional grapheme, sputtering time 1-10min;, finally give three-dimensional grapheme-Si-MoS2Composite.
- 7. three-dimensional grapheme-Si-MoS according to claim 62The preparation method of composite, it is characterised in that described Working gas is Ar gas.
- 8. three-dimensional grapheme-Si-MoS according to claim 12The preparation method of composite, it is characterised in that described Three-dimensional grapheme is prepared to comprise the following steps that:1) substrate is provided;2) under the conditions of the protection gas and hydrogen that flow velocity is 300-600s.c.c.m, 800~1300 DEG C of temperature, substrate surface is removed Carbon-source gas are passed through after oxide skin(coating) again, 2-10 closes carbon-source gas after minute, by obtained sample using cooldown rate as 200- 300 DEG C/min is cooled to room temperature, closes protection gas and hydrogen;3) PMMA in the coating of the surface of obtained sample, then puts it into metal etch liquid and removes metallic substrates, then use Deionized water rinses;4) above-mentioned sample is put into acetone or toluene, PMMA is removed, then with ethanol, deionized water successively soaking and washing;5) finally the sample cleaned up is freeze-dried, obtains the three-dimensional grapheme of structural integrity.
- 9. three-dimensional grapheme-Si-MoS according to claim 82The preparation method of composite, it is characterised in that described Carbon-source gas be methane, methanol, ethanol or ethane in one or more, described protection gas is argon gas or neon.
- 10. three-dimensional grapheme-Si-MoS according to claim 82The preparation method of composite, it is characterised in that described Metal etch liquid is FeCl in step 3)3Solution, ammonium persulfate or HCl and H2O2Mixed solution.
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PCT/CN2017/095364 WO2018024182A1 (en) | 2016-08-01 | 2017-08-01 | Method for preparing three-dimensional graphene-si-mos2 composite material |
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CN108598406A (en) * | 2018-04-18 | 2018-09-28 | 中航锂电技术研究院有限公司 | Carbon coating MoS2The preparation method and application of/silicon composite |
CN109686954A (en) * | 2018-12-27 | 2019-04-26 | 陕西科技大学 | A kind of C-O-Mo key bridge joint monolithic taper MoS2/ NG sodium ion negative electrode material and preparation method thereof |
CN111987291A (en) * | 2020-08-07 | 2020-11-24 | 河北大学 | Preparation method of metal sulfide composite electrode for electrochemical lithium storage |
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CN114084876B (en) * | 2021-11-22 | 2023-09-01 | 乌海瑞森新能源材料有限公司 | One-dimensional multilayer nano-chain composite material, preparation method thereof and application thereof in lithium ion battery |
CN116072879B (en) * | 2023-04-07 | 2023-07-07 | 河南工学院 | Electrode material of lithium ion battery and preparation method thereof |
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CN108598406A (en) * | 2018-04-18 | 2018-09-28 | 中航锂电技术研究院有限公司 | Carbon coating MoS2The preparation method and application of/silicon composite |
CN109686954A (en) * | 2018-12-27 | 2019-04-26 | 陕西科技大学 | A kind of C-O-Mo key bridge joint monolithic taper MoS2/ NG sodium ion negative electrode material and preparation method thereof |
CN111987291A (en) * | 2020-08-07 | 2020-11-24 | 河北大学 | Preparation method of metal sulfide composite electrode for electrochemical lithium storage |
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